Chromium and cobalt complex compounds of monoazo dyestuffs



United States Patent "ice 3,144,437 CHROMIUM AND COBALT COMPLEX COM-POUNDS OF MONOAZO DYESTUFFS Hanspeter Uehlinger, Binningen, Switzerland,assignor to Sandoz A.G., Basel, Switzerland No Drawing. Filed July 10,1958, Ser. No. 747,570 Claims priority, application Switzerland Mar. 15,1957 6 Claims. (Cl. 260-147) This application is a continuation-in-partof the US. application, Serial No. 720,015, filed March 10, 1958, nowabandoned.

This invention relates to the chromium and cobalt complex compounds ofmonoazo dyestuffs of the general formula wherein x stands for asubstituent in ortho-position to the azo group capable of taking part inmetal complex formation,

y a hydrogen atom or a methyl group,

A the radical of a diazo component of the benzene series which may carrynon-ionic substituents, and

R a mononuclear or dinuclear aromatic radical which may carry non-ionicsubstituents.

Especially valuable dyestuffs are the chromium and cobalt complexcompounds of the monoazo dyestuffs of the general formula '3: CH to (II)wherein z-H represents a hydroxy or carboxy group,

w represents a hydrogen atom or a sulfonic acid-amide group, which maybe further substituted, and

v represents a hydrogen or a chlorine atom.

The process for the production of the new metal complex compounds ofmonoazo dyestuffs consists in coupling 1 mol of the diazo compound of anaminobenzene which contains in ortho-position to the amino group asubstituent capable of taking part in metal complex formation but isfree from carboxylic acid groups in metaor para-position to the aminogroup and from sulfonic acid groups with 1 mol of a S-aminopyrazole ofthe general formula 3,144,437 Patented Aug. 11., 1964 acetylamino,carbornethoxyamino, carbethoxyamino, methyl, ethyl, tert.butyl,me'thoxy, sulfonic acid-amide, sulfonic acid-methylamide, sulfonicacid-dimethylamide, sulfonic acid (2 hydroxy) ethylamide, sulfonicaciddi(2'-hydroxyethyl)amide, sulfonic acid-hydroxypropylamide, sulfonicacid-methoxypropylamide, sulfonic acidphenylamide, methylsulfonyl andethylsulfonyl groups.

The aminobenzenes are diazotized in the normal manner at 0 to 5 C. Theresultant diazo compounds are coupled with the coupling components ofFormula III at 10 to 40 C. in a weakly acid medium, if desired inpresence of a tertiary base like pyridine. The monoazo dyes thus formedare, if necessary, precipitated from the coupling mass by means ofcommon salt or acid and then filtered oif, washed and dried.

Chromium or cobalt compounds are preferred for converting the monoazodyestuffs into their metal complex compounds. Metallization is bestcarried out in an aqueous solution or an organic medium, for exampleformamide, dimethylformamide, ethylglycol, or in the concentratedaqueous solution of an alkali metal salt of a low molecular aliphaticmonocarboxylic acid. It is desirable to proportion the reactants so thatless than two but at least one metal atom acts upon two molecules of themonoazo dyestuff.

Suitable chromium compounds are, e.g., chromic fluoride, chromicsulfate, chromic formate, chromic acetate, potassium chromic sulfate andammonium chromic sulfate. The chromates also-e.g., sodium and potassiumchromate or bichromate-are eminently suitable for metallizing themonoazo dyestuffs. In this last case it is advisable to conduct thereaction in a strongly caustic alkaline solution, to which reducingsubstances may be added if desired.

Cobaltous formate, cobaltous acetate and cobaltous sulfate serve ascobalt compounds. When metallization is carried out in the concentratedaqueous solution of an alkali metal salt of a low molecular'aliphaticmonocarboxylic acid, water-insoluble metal compounds such as cobalthydroxide and cobalt carbonate may be used as alternatives.

It is of particular advantage to conduct metallization in an aqueous oralkaline medium, the metal compounds being added in the presence ofcompounds which keep the metal dissolved in complex combination incaustic alkaline medium. Examples of such compounds are tartaric acid,citric acid and lactic acid.

The metal complex compounds thus obtained are precipitated from aqueousmedium by the addition of salt; if desired the organic metallizingsolution may be previously run into water. The precipitate is filtered,washed if desired and dried.

The resultant metal-containing azo dyestuffs are h0- rnogeneous metalcomplex compounds in which essentially one atom of metal is combinedwith two molecules of the monoazo compound. They are commonly termed 1:2complexes wherein 1 molecule of the monoazo compound is combined withapproximately 0.3 to 0.7 atom of metal.

The new chromiumor cobalt-containing azo dyestufis dye wool, silk,leather and polyamide fibers from neutral or weakly acid dyebaths inorange, brown, brownred and bordeaux shades, which are fast to washing,milling, perspiration, alkali and acids and very fast to light. Thosewhich have sufficiently high solubility in organic solvents-likeacetone, ethyl alcohol, ethyl acetate, tetrahydrofuran,dimethylformarnide are also suitable for dyeing artificial fibers in themass, i.e., in solutions with organic solvents, prior to spinning intofilament; they are also of interest for coloring paint and lacquer mediaand plastic moulding compounds. The thus dyed materials exhibit goodfastness to light and wet treatments.

In the following examples all parts and percentages are by weight. Thetemperatures are given in degrees centigrade.

Example 1 of crystallized sodium acetate and 7 parts of crystallizedchromic potassium sulfate the solution is heated to 94-96 and thistemperature maintained for 8 hours. The product, a chrome-containingdyestuff, is isolated as described i bers 26.4 parts of2-amino-1-hydroxybenzene-4-sulfon1c 522 5 5 5 g ggg wfi 322 23:22 fiacid-phenylamide and 8 parts of sodium hydroxide are g D dissolved in130 parts of water. After the further addi- Example 3 tion of 6.9 partsof sodium nitrite in 25 parts of water 202 parts of 1 4 lf i theresultant solution is run into a mixture of 48 parts of acid methylamideare dissolved in a mixture of 20 pal-ts concentrated hydrochloric acidand 100 parts of ice, the 10 of 30% hydrochloric acid and 500 Parts ofwater. The temperature of the latter being not highs? than solution iscooled to 0 and a solution of 6.9 parts of parts of 1'Phenyl'3'methy1'5'ammop yrazqlg l sodium nitrite in 20 parts of water is added slowlywith dissolved in 18 parts of concentrated hydrochloric acid stirring,the temperature being maintained at about r t, and 200 parts of waterand added to the diazo suspension. r when the diazotization is completedthe diazo 5115mm- After the addition of 50 Parts of pyridin"? thacoupling 10 sion is run into a solution of 17.3 parts of l-phenyl-3-mass is heated to 35-400. and held thls temysratullemethyl-S-aminopyrazole in 18 parts of concentrated hyfor 8 wmPletmn P 3the 11mm drochloric acid and 200 parts of water. After the addi- Souredto react acid on Congo red mdlcator Paper upon tion of 70 parts ofpyridine the coupling mass is heated to which the precipitated dyestulfis filtered 01f, washed 0 and Stirred at 35 40:: for 8 hours with Waterand dried The formed monoazo dyestulf is precipitated by sour- 9 Partsof the monoazo compound are l F m 90 ing the coupling mixture to reactacid on Congo red Parts of formamlde at 80 and after the addltlon of 7indicator paper, then it is filtered olf, washed with cold parts ofcrystallized sodium acetate and 3.6 parts of water dried and groundcrystallized cobaltous sulfate the solution is maintained chromiumcomplex compound obtained by treat. at 94-9? for 8 f this time 85 partsof a 25 ing the monoazo compound with chromic potassium sulcommon Saltare added The comPletely fate or chromic ammonium sulfate according tothe parcipitated dyestuffs. Washeq fi. 10% ticulars of Example 2 is abrown powder which dyes 9 salt Solunon and fi on gnndmg It IS wool, silkand synthetic polyamide fibers in brownish tamed as a brown powderpossesses good ammty red shades possessing good fastness to light,washing, for wool, silk, leather and polyamide fibers. It dyes thesemining perspiration alkali and acids fibers in yellowish brown shades ofgood fastness to light The cobalt comlex compound may be prepared as andwet agencies. Its solubility in acetone at 20 amounts follows: to 20grams Per liter 9 parts of the monoazo compound are dissolved in partsof.the cob2.!1t'contammg azo dyesmfi thus ob- 100 parts of ethylglycolat 80 and after the addition of talmid are dlssolved m 4000 Parts ofwater at 7 arts of crystallized sodium acetate and 3.6 parts of 1 pleceof .scoured Wool 100 parts by welght crystallized cobaltous sulfate thesolution is maintained P l mm the Whlch 2 Parts 9 100% at 94-97 for 8hours. After this time 85 parts of a he acid dropwlse' The qyebath ISheilted 25% common salt solution are added. The completely to the i Inthe course of Inmates and mamtamqd 40 precipitated dyestulf is filteredoff, washed with a 10% at the boll for .another. mmutes' rljhe Woolcommon salt solution and dried. On grinding it is obthen removed, rinsedwith water and dried. It is dyed lIl tamed as a brown powder whichpossesses good affinity a fast shade of brown for W001, silk, leatherand polyamide fibers. It dyes these Example 2 fibers in yellowish brownshades of good fastness to light 23 parts of2-amino-1-carboxybenzene-S-sulfonic acid- 45 and wet agencies. In saltfree form it possesses a solumethylamide and 20 parts of sodiumcarbonate are diS- bility of grams per liter of acetone at 20. solved in300 parts of water. 6.9 parts of sodium nitrite F th chromiumndcobalt-containing azo dyestufls in 25 parts of water are added and thesolution is then which are obtainable according to the particulars givendropped into parts of concentrated hydrochloric acid in Examples 1 to 3are set out in the table below. They and 160 parts of Water at 05. 0.7parts f 1-(3'- 50 are characterized by the diazo and coupling componentschloro)-phenyl-3-rnethyl-5-aminopyrazole are dissolved in (columns (I)and (11)), the form in which they are 18 parts of concentratedhydrochloric acid and 200 parts ap lied (HI) and the shade of themetallized dyeing on of water and added to the diazo solution. Thecoupling wool (IV). mass is adjusted to pH 6 with soda and agitated for12 hours at 20. The dyestuff thus formed is precipitated, Theabbrevlatlonsm Column (In) stand filtered off, washed with water anddried. 0 Afterchr.=afterchroming dyestulf 9 parts of the monoazocompound are dissolved in 90 Cr-C=chrome-complex dyestufif parts offormamide at After the addition of 7 parts C0-C=cobalt-complex dyestutfTABLE Example Diazo component Coupling component Form in Shade ofmetallized N 0. which applied dyeing on woolZ-amino-l-hydroxybenzene-5su11'onic acidrncthylamide.

l-plionyLB-methyl-5-arnln0pyrazo1o Yellowish brown. Brownish Bordeaux.

2-amino-1-hydroxybenzene-4-sulfonic-aciddo Brownish red.

(El-mothoxy)-propylan1ide. Yellowish brown.2-amino-1-hydroxybcnzenei-sulfonic acid- -do Yellowish brown.

amide. Brownish red. 2-amino-1-carboxybenzcne-s-sultonic aciddo Orange.amide. Brow-n. 2-amino-1-earboxybenzene-5-sul1'onic aeid- 1-(3e11loro-)-pheuyl-3-1ncthyLS-aminopyrazole Orange. phenylamide. Brown.Zamino-l-hydroxybenzene-5-sultonic aciddo Yellowish brown.

mcthylarnrde. Brownish Bordeaux. 2-amino-l-hydroxybenzene-tsullonicaeiddo Brownish red. methylamide. Yellowish brown. 11Z-ZlmlIlGJ-hydrOXYbI-BHZGHG-4-Sllll'01110 aciddo 1 Ycllowish brown.

(2'-hydroxy)-ethylan1lde.

Brownish red.

TABLEC0ntinued Dlazo component Coupling component Form in which applied(III) Shade of metallized dyeing on wool2-arnlno-l-hydroxybenzenei-sulfonic acidethylamide.Z-amino-1-hydroxybenzene-4-sulfonic acidam e.2-amino-l-hydroxybenzenei-sulfonic acid- (2-eth02gy)-ethylamide.2-amino-1-hydroxybenzenei-sulfonic acidphenylamide.Z-amino-l-hydroxybenzene-4-su1tonic acidmethylarnide.2-arnino-1-hydroxybonzenei-sulfonic acid- (2-hydroxy)-propylan1ide.Z-amino-l-hydroxybenzene-4-sulfomc aardamide.2-amino-1-hydro1rybenzene-4-su1f0n1c acldisopropylamide.Z-amino-l-carboxybenzene-fi-sulfonic aerdmelthylamide. o

2-amin0-1-hydroxybenzene-5-sulfonic acidbutylamide.2-amino-1-hydroxybenzene-4-su1f0mc acldam e.

2-amino-1-hydroxybenzene-4-su1fonic acid- (3-isopropoxy) -propy1am1de.

2-amin0-1-hydroxybe11zene-4-su1fonio acld- (4-methyl)-pheny1amide.

2-arnino-1-hydroxy-4-ethylsulfonylbenzene.

2-arnino-1-hydroxybenzenei-sulfonic acidethylamlde.

Z-amino-l-hydroxybenzene-4-sulfon1c acrddi-(2-hydroxy)-ethylamide.

Z-aminoJ-hydroxyi-chlorobenzene 2-amino-1-hydroxybenzene-l-sulfonicacidcyclohexylamide.

2-aminobenzene-1-carboxylic acld 2-amino-1-hydroxy-4-nitrobenzone2-amino-l-hydroxy-4-nitro-6-ch1orbenzene 2-amino-l-hydroxybenzene2-amino-1-hydroxyA-methyl-bcnzene Z-amino-1-hydroxy-4-acetylaminobenzene2-amino-l-hyrdoxybenzenei-sulfonic acidphgnylamide. o

Z-amino-l-hydroxybenzene-i-sulionic acidbenzylamide.

z-amino-l-hydroxybenzene-et-sulfome acid-(4- methoxy)-pheny1amide.

2-amino-1-hydroxybenzene-i-sulfonic aoldamide.

2-aminobenzene-l-carboxylic acid 2-amino-5-nitrobenzene-1-carboxy1icacid Z-aminobenzene-l-carboxylic vid 1-pheny1-3-methy1-5-aminopyrazo1e1-(3eh1or0-)-pheny1-3-methy1-5-aminopyraz01e1-(4-chloro)-phenyl-3-methy1-5-an1inopyrazo1e-1-(2.5-dichloro)-phenyl-3-methy1-5-aminopyrazole. .do

1-(4-methy1)-pheny1-3-methyl-5-aminopydrazole. o

1-pheny1-3-methy1-5-amino-pyrazo1e-3-su1fonic acidamide.

l-(4-methy1)-pheny1-3-methyl-5-aminopyrazole.

1-phenyI-B-methy1-5-amin0-pyraz01e-3-sulf0nic acidamidel-pheny1-3-methy1-5-amino-pyrazo1e-3-su1fonic acidamide.

acgd-phenylamidc. o

1-(3-ch1oro)-phenyl-3-methy1-5-aminopyrazo1-phenyl-B-methyl-5-amino-pyrazo1e 1-(3-methy1su1ony1)-pheny1-3-methyl-5- aminopyrazole.

1-(2.5-dioh1oro)-pl1eny1-3-methyl-S-aminopyrazole1-(3-ehloro)-pheny1-3-methy1-5-aminopyrazo1e.

2-amino-1 carboxybenzene-fieulfonic acidphenylamide. z-am'mo-1-hydroxy-4-ch1orobenzene-fi-sulfonie acd-phenylamlde. o

2-amino-l-hydroxybenzenei-sulfonic acid- (3-methoxy)-pr0py1amide.Z-amino-l-hydroxybenzene-4-sulfonic acrdphenylamide.2-amino-l-hydroxybenzene-5-su1fonic acldamide.2-amino-1-hydroxybenzene-fi-sulfonic aard- (2'-hydroxy)-ethylamide.Z-amino-l-hydroxybenzene-4-su11'onic acld- (3-methoxy)-propy1arnide.Z-arnino-l-hydroxybenzene4-su1fon1c acuimethylamide.2-amin0-1-hydroxybenzene-4-sulfomc aerdphgnylamide. o

2-amino-l-hydroxy-4-chloro-fi-nitrobenzene-Z-ami110-1-hydroxy-4.6-dieh1orobenzeneZ-amino-l-hydroxy--chlorobenzene-5-su1fonic acidethylamide. v

2-aminobenzene-1-ca.rboxyl1c acldZ-amino-l-hydroxy-4-methyl-G-nitrobenzene.

1-phenyl-B-mothyl-S-aminopyrazole1-(3ich1oro)-pheny1-3-methyl-5-aminopyrazo e1-(2.5-dich10ro)-phenyl-3-mothy1-5-ami;no-

pyrazole. 1-(8'-chloro) phenyl-5-aminopyrazole1-(4-methy1)-phenyl-5-aminopyrazole1-(2.5-dieh1oro)-phenyl-5-aminopyrazole1-(4-c1110r0)-phenyl-5-aminopyrazo1e l-phenyl-5-aminopyrazo1e1-pheny1-5-arnjnopyrazo1e-3-su1fonic acidphdenylamide. o

l-pheny1-5-aminopyrazo1e-4-su1ionic acid-(3"- methoxy)-buty1amide.l-phenyl-fi-aminopyrazole Brownish red.

Brownish red. Yellowish brown. Yellowish brown. Brownish red. Yellowishbrown. Brownish red. Brownish red. Yellowish brown. 7 Yellowish brown.

Browrrish red. Brownish red. Yellowish brown. Yellowish brown. Brownishred. Brown.

Orange.

Orange.

Brownlsh red. Yellowish brown. Yellowish brown. Brownish red. Brownishred. Yellowish brown. Yellowish brown. Brownish red. Brownish red.Yellowish brown. Yellowish brown. Brownish red. Brownish red.

Brownish red. Yellowish brown. Brownish red.

Brown. Orange. Brownish red.

Brownish red. Yellowish brown. Yellowish brown. Brownish red. 'Brownishred. Yellowish brown. Yellowish brown. Yellowish brown. Yellowish brown.Brownish red. Brownish red. Yellowish brown. Yellowish brown. Brownishred. Yellowish brown. Brownish red. Brownish red. Yellowish brown.Brown.

Orange.

Orange.

Brown.

Brown.

Orange.

Orange.

Brown.

Orange.

Brown. Yellowish brown.

Yellowish brown. Yellowish brown. Brownish red Brownish red. Yellowishbrown.

Yellowish brown. Yellowish brown.

Brownis h red. Yellowis h brown. Yellowish' brown.

Yellowish brown. Brownish red. Brownish red. Yellowish brown. Yellowishbrown. Brownish red. Yellowish brown. Brownish red. Brownish red.

Yellowish brown. Brown. Orange Browni sh red.

Brown. Brownish Bordeaux.

Brow-nish Bordeaux. Brownish Bordeaux.

Brownish Bordeaux.

Brownish Bordeaux.

Brownish Bordeaux.

TABLE-Continued Example Dlazo component Coupling component Form in Shadeof metallized N 0. which applied dyeing on wool (I) (II) (III) (IV) 652-amlno-1-hydroxy-4-tert. butylbeuzene1-(3-met{10xy)-phenyl-3-methyl-5-amino- Brownish red. pyrazo e. 66Z-amino-l-hydroxy-4-nitrohenzene 1-(4-Ineth0xy)-phenyl-5-aminopyrazoleBrownish red.

Yellowish brown. 67 Z-amino-l-hydroxyA-bromobenzene1-(4-acety1amino)-pl1eny1-3-methyl-fi-amino- Yellowish brown.

pyrazolc. Brownish red. 68 Z-amirgjo-thycroxybenzenc-4-sulfonic acid- 1-(3-nitro) -phenyl-3-methyl-5-aminopyrazo1e Brownish red.

rnet y mi e. 69 i do l-naphthyl-(1)-3-methy1-5-am1nopymzolc4- Brownishred.

sulionic acid-amide. 70 2-amino-1-hydroxy-4-bromobenzene1-naphthy1-(2)-3methy1-5-aminopyrazolc6- Brownish red.

sull'onic acid-amide. 71 2amlno-l-hydroxybenzene--su]Ionic aeid-1-(2'.3-tetramethylene)-pheny15-aminopyraz- Brownish red.

amide, ole-4-sullonic acid-dimethylamide. Yellowish brown. 72 do 1-(2.1?-tetramethylene)-phenyl-3-rnetl1yl-5- Brownisll red.

aminopyrazole-4-sullonic acid-mothylamide. Yellowish brown. 732-amino-1-hydroxy-4-methyl-sultonylummo-1-(3-bromo)-phenyl-3-methyl-5-amino- Yellowish brown,

benzene. pyrazole. 74 Z-nmino-l-hydroxy-4-chloro-fi-nitrobeuzeue.1-(4'-nitro)-phenyl-5-aminopyrazole Yellowish brown.

Browmsh red. 75 rln 1-(3-acetylammo)-phenyl-5-aminopyrazolc Brownishred.

Yellowish brown. 76 Z-aminobenzene-l-earhoxyhc acid1-(3'methylsulfonylamino)-phenyl-5-amino- Orange. pyrazole. Brown. 772-arnino-1-carboxyheuzeue-S-sulfomc acldl-phenyl-S-ammopyrazole Orange.phenylamide. Brown. 78 Z-amino-l-earboxybenzene-S-sulfouic actd-1-(4-pheny1su1f0nylamino)-pheny1-3-metl1y1- Orange.

amid -aminopyrazolc.

Example 79 Example 3 100' parts of secondary cellulose acetate with acontent of 54-55% of splittable acetic acid are dissolved in 300 CH NHOS 0 parts of a solvent (e.g., a mixture of 275 parts of acetone and 25parts of methanol). After homogeneous mixmg N the mass is left overnightto swell. Next day 1 part of H the cobalt complex dyestulf obtainedaccording to Ex- III ample 3 is dissolved in 60 parts of the samesolvent. This Cr solution is added to the cellulose acetate solution andthe NH whole is agitated long enough for 60 parts of the solvent toevaporate. N N

The dyed acetate solution is filtered through a cotton filter and acotton wool pressure filter before entering the spinning unit. The finalphase of the operation to the formation of the dyed filament, is thesame as in the pro- 9 duction of undyed cellulose acetate.

Formulae of representative dyestuffs of the foregoing examples are asfollows:

Example 1 O 3HNO$ o x 1 ii f H3CC-C CO 11* f o Co 11+ /CNH n c- (|3NH NExample 2 Example 39 F CH;HNO2

HN-OzS O CO-0 N N H II N N 5 2: Cr II+ Cr 11* Inc-c CNH Inc-("3 CHN- IQTl --N NN CI 2 J2 J 9 Example 40 meme- 30 Example 47 Having thusdisclosed the invention, what is claimed is:

1. A metal complex dyestufi which corresponds to the 2 is a bridginglink selected from the group consisting w is a member selected from thegroup consisting of a hydrogen atom, a lower alkyl sulfonyl, a sulfonicacid lower alkyl amide, a sulfonic acid lower oxyalkyl amide, and asulfonic acid mononuclear aryl amide group,

v is a member selected from the group consisting of a hydrogen atom anda chlorine atom, and

Me is a metal atom selected from the group consisting of a chromium anda cobalt atom.

2. The cobalt complex dyestuif which corresponds to the formula 3. Thechromium complex dyestutf which corresponds to the formula 6. Thechromium complex dyestuff which corresponds to the formula ReferencesCited in the file of this patent UNITED STATES PATENTS Taube et al. May13, 1941 Zickendraht Nov. 26, 1957 OTHER REFERENCES Venkataraman:Synthetic Dyes, vol. I, p. 540 (1952).

1. A METAL COMPLEX DYESTUFF WHICH CORRESPONDS TO THE FORMULA